U.S. patent application number 11/330004 was filed with the patent office on 2006-06-01 for methods for cleaning a substrate.
Invention is credited to Yoichi Isago, Naoaki Kobayashi, Shu Nakajima, Kazuo Nojiri, Teruo Saito.
Application Number | 20060112974 11/330004 |
Document ID | / |
Family ID | 19091202 |
Filed Date | 2006-06-01 |
United States Patent
Application |
20060112974 |
Kind Code |
A1 |
Isago; Yoichi ; et
al. |
June 1, 2006 |
Methods for cleaning a substrate
Abstract
The invention provides a water supplying apparatus and method
thereof which has a high capacity of peeling and removing a disused
material such as a resist film and the like, and can efficiently
use water vapor. A water supplying apparatus for executing a
washing process, a cleaning process and a working process of a
subject, is provided with a water vapor body supplying means for
supplying a water vapor body, and a water mist body supplying means
for supplying a water mist body containing liquid water fine
particles, and the structure is made such that said water vapor
body and said water mist body are supplied to the subject by
independently controlling said two means.
Inventors: |
Isago; Yoichi; (Kanagawa,
JP) ; Nojiri; Kazuo; (Tokyo, JP) ; Kobayashi;
Naoaki; (Chiba, JP) ; Saito; Teruo; (Chiba,
JP) ; Nakajima; Shu; (Kanagawa-ken, JP) |
Correspondence
Address: |
IPSG, P.C.
P.O. BOX 700640
SAN JOSE
CA
95170-0640
US
|
Family ID: |
19091202 |
Appl. No.: |
11/330004 |
Filed: |
January 10, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10229931 |
Aug 27, 2002 |
7004181 |
|
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11330004 |
Jan 10, 2006 |
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Current U.S.
Class: |
134/31 ;
134/100.1; 134/102.1; 134/198; 134/34 |
Current CPC
Class: |
B08B 3/00 20130101; G03F
7/422 20130101; B01F 3/022 20130101; B05B 7/0433 20130101; Y10S
134/902 20130101; B05B 7/0475 20130101; B01F 3/04049 20130101; H01L
21/67051 20130101; B01F 2215/0096 20130101; B08B 3/02 20130101;
B01F 2215/0045 20130101; B01F 5/045 20130101; B05B 7/066 20130101;
B05B 7/065 20130101 |
Class at
Publication: |
134/031 ;
134/034; 134/198; 134/102.1; 134/100.1 |
International
Class: |
B08B 3/02 20060101
B08B003/02 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 31, 2001 |
JP |
2001-264627 |
Claims
1-16. (canceled)
17. In a substrate processing chamber, a method for cleaning a
substrate having one of a resist film and a polymer residue on a
surface of said substrate, comprising: providing a water vapor
producing arrangement that includes at least a heating arrangement
for heating water to produce water vapor and a first aperture
configured to supply said water vapor at a first temperature to
said surface of said substrate; and providing a water mist
producing arrangement including at least a second aperture
configured to supply a water mist containing water particles to
said surface of said substrate, said water mist being supplied to
said surface substrate at a second temperature lower than said
first temperature; and supplying one of said water vapor and said
water mist to said surface of said substrate to at least partially
clean said substrate with said one of said water vapor and said
water mist.
18. The method of claim 17 further comprising supplying a gas along
with least one of said water vapor and said water mist containing
said water particles, said gas being supplied through said first
aperture if said gas is supplied along with said water vapor, said
gas being supplied through said second aperture if said gas is
supplied along with said water mist.
19. The method of claim 17 further comprising setting said first
temperature such that said water vapor becomes suitable for
permeating one of a resist film and a polymer residue that is
disposed on said substrate to accomplish said cleaning.
20. The method of claim 17 further comprising setting a flow rate
of said water mist such that said water mist becomes suitable for
physically peeling one of a resist film and a polymer residue that
is disposed on said substrate.
21. The method of claim 17 wherein said first temperature is at
least equal to a boiling point of said water.
22. The method of claim 21 wherein said second temperature is at
most equal to said boiling point of said water.
23. In a substrate processing chamber, a method for cleaning a
substrate having one of a resist film and a polymer residue on a
surface of said substrate, comprising: providing a water vapor
producing arrangement that is configured to supply water vapor to
said surface of said substrate through a first nozzle, said water
vapor being produced using water at a first water usage rate;
providing a water mist producing arrangement configured to supply
water mist to said surface of said substrate through a second
nozzle different from said first nozzle, said water mist being
produced using said water at a second water usage rate higher than
said first water usage rate, thereby enabling said water mist to
exert a greater peeling force on said surface of said substrate
than a peeling force exerted by said water vapor; and supplying at
least one of said water vapor and said water mist to said surface
of said substrate to at least partially clean said substrate with
said one of said water vapor and said water mist.
24. The method of claim 23 wherein said water vapor producing
arrangement further includes a heating arrangement configured to
furnish said water vapor at a first temperature that is higher than
a second temperature associated with said water mist, thereby
enabling said water vapor to permeate said one of said resist film
and said polymer residue on said surface of said substrate to a
greater extent than said water mist.
25. The method of claim 23 further comprising supplying a gas with
said water vapor prior to subjecting said surface of said substrate
to said water vapor, said gas being one of air, nitrogen, carbon
dioxide, ozone, argon, and helium, said gas being ejected out of
said first nozzle along with said water vapor at said surface of
said substrate.
26. The method of claim 23 wherein said supplying said at least one
of said water vapor and said water mist to said surface of said
substrate includes supplying both said water vapor and said water
mist simultaneously to said surface of said substrate.
27. The method of claim 23 wherein said supplying said at least one
of said water vapor and said water mist to said surface of said
substrate includes supplying both said water vapor and said water
mist to said surface of said substrate, said water vapor being
supplied to said surface of said substrate at a time that is
different from a time that said water mist is supplied to said
surface of said substrate.
28. The method of claim 27 wherein said water vapor is supplied to
said surface of said substrate before said water mist is supplied
to said surface of said substrate.
29. The method of claim 23 wherein said substrate processing
chamber includes a pressure controlled inner portion capable of
maintaining at least one of an atmospheric pressure state, a
depressurized state, and a pressurized state.
30. The method of claim 23 wherein said water vapor producing
arrangement further includes a heating arrangement that is
configured to produce said water vapor at a first temperature that
is at least equal to a boiling point of said water, and wherein
said water mist producing arrangement is configured to produce said
water mist at a second temperature that is at most equal to said
boiling point of said water.
31. In a substrate processing chamber, a method for cleaning a
substrate, comprising: providing a water vapor producing
arrangement that is configured to supply water vapor and a gas
(water vapor/gas) at a first temperature to said surface of said
substrate through a first nozzle, said water vapor being produced
using water at a first water usage rate; providing a water mist
producing arrangement configured to supply water mist to said
surface of said substrate through a second nozzle different from
said first nozzle, said water mist being produced using said water
at a second water usage rate higher than said first water usage
rate, said water mist being at a second temperature that is lower
than said first temperature; and supplying at least one of said
water mist and said water vapor/gas to said surface of said
substrate to at least partially clean said substrate with said one
of said water mist and said water vapor/gas.
32. The method of claim 31 wherein said gas is one of air,
nitrogen, carbon dioxide, ozone, argon, and helium.
33. The method of claim 31 wherein said water mist is suitable for
physically peeling from said surface of said substrate one of a
resist film and a polymer residue.
34. The method of claim 31 wherein said water vapor/gas is suitable
for permeating said one of a resist film and a polymer residue,
said one of a resist film and a polymer residue being disposed on
said surface of said substrate.
35. The method of claim 31 wherein said first temperature is at
least equal to a boiling point of said water, and said second
temperature is at most equal to said boiling point of said
water.
36. The method of claim 31 wherein said supplying said at least one
of said water mist and said water vapor/gas includes supplying both
said water vapor/gas and said water mist to said surface of said
substrate, said water vapor/gas being supplied to said surface of
said substrate at a time that is different from a time that said
water mist is supplied to said surface of said substrate.
37. The method of claim 36 wherein said water vapor/gas is supplied
to said surface of said substrate before said water mist is
supplied to said surface of said substrate.
Description
REFERENCE TO RELATED APPLICATION
[0001] This application claims the priority right of Japanese
Patent Application No. 2001-264627 filed on Aug. 31, 2001, the
entire disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to an apparatus for supplying
water (H.sub.2O) in a manufacturing process of a product, and
relates to an apparatus for supplying high purity water used for a
working process of a product surface and a washing and cleaning
process thereof. More particularly, the present invention relates
to a water supplying apparatus and a method thereof for peeling out
a disused material such as a resist film, a polymer residue or the
like attached to a subject surface such as a semiconductor wafer, a
hard disc (HD), a liquid crystal display (LCD), a flat panel
display (FPD) or the like in a lithography process so as to
remove.
[0004] 2. Description of the Related Art
[0005] In a manufacturing process of a semiconductor apparatus, a
liquid crystal display, a magnetic disc, a printed circuit board or
the like, a resist is applied to a surface of the subject and a
high-precision process such as a pattern forming or the like is
applied to the surface of the subject by using a lithography.
Thereafter, a process of removing the disused material such as the
resist film, the polymer residue or the like attached to the
surface of the subject is executed.
[0006] As a technique of removing the disused material such as the
resist film or the like which has been conventionally executed,
there are a plasma asher method of ashing and removing the resist
film by oxygen plasma, a method of thermally removing a film body
by an organic solvent (a phenol solvent, a halogen solvent or the
like), a thermally dissolving method executed by concentrated
sulfuric acid and hydrogen peroxide, and the like.
[0007] However, in any of the methods mentioned above, a time, an
energy and a chemical material for disassembling and dissolving the
resist film and the like are required, and a load in the process of
disassembling and dissolving the resist film and the like is great.
The plasma asher method is generally well known, however, there is
a problem that a charge-up damage generated by charged particles is
great. Further, since there is a problem that it is impossible to
sufficiently remove a reaction product (a polymer residue)
generated in an etching process, it is necessary to wet remove
this, so that there is a problem that a number of processes is
increased. Accordingly, in a field of a precision surface treatment
technique including a technique of removing the disused material
such as the resist film and the like, a great attention is paid to
a method of using water and water vapor which are rich in the
natural world, as a technique casting off from the prior art using
the chemical material and the chemical process and being gentle for
the earth and the environment, and there is an expectation of using
and developing the technique.
[0008] A technique of removing the resist film remaining on the
surface of the semiconductor apparatus, the liquid crystal device
or the like by using the water vapor is described in Japanese
Unexamined Patent Publication No. 2001-118817. In accordance with
the publication mentioned above, there is disclosed a technique of
lifting off the residual resist film from the surface of the
subject by high temperature mist in the water vapor so as to remove
it.
[0009] However, in order to completely peel out and remove the
resist film, it is necessary to generate a lot of water vapor, so
that there is a disadvantage that an electric power consumption is
too large.
[0010] As a result of devoting themselves to and taking into
consideration a mechanism of peeling out and removing the resist
film by using the water vapor, the inventors of the present
application have noted that the peeling and removing process of the
resist film is constituted by the following two steps.
[0011] That is, at first, vaporized water (this is called as a
water vapor body) permeates through the resist film so as to reach
an interface between the resist film and the surface of the
subject, thereby weakening a bonding force of the resist film on
this interface and floating the resist film from the surface of the
subject (lifting off).
[0012] Next, mist-like water containing liquid water fine particles
together with a predetermined injection pressure (this is called as
a water mist body) physically acts on the lifted off resist film so
as to peel out the resist film from the interface.
[0013] Since the water vapor body and the water mist body have
different roles in the peeling and removing process of the resist
film as mentioned above, if it is possible to control the water
vapor body and the water mist body most appropriately so as to
generate them, a lot of water is not required and it is possible to
reduce electric power consumption.
[0014] That is, the water vapor body requires an application of a
high temperature and a high energy for the purpose of permeating
through the resist film, however, the amount to be required is a
little. Accordingly, it is possible to generate the water vapor
body by a little electric power consumption.
[0015] On the contrary, since the water mist body is used for
physically peeling out the lifted off resist film, the amount to be
required is more than that of the water vapor body, however, it is
not necessary to heat to a high temperature, and it is only
necessary that a predetermined injection pressure is applied, so
that the electric power consumption for the generation is hardly
required.
[0016] In this regard, in the method of utilizing the water vapor
described in the publication mentioned above, since the water mist
body and the water vapor body exist in a mixed state without being
controlled to the respective optimum conditions, efficiency has
been deteriorated.
SUMMARY OF THE INVENTION
[0017] The present invention is made on the basis of the knowledge
mentioned above, and an object of the present invention is to
provide a water supplying apparatus and method thereof which has a
high capacity of peeling and removing a disused material such as a
resist film, a polymer residue and the like, and can efficiently
remove the disused material.
[0018] The water supplying apparatus in accordance with the present
invention employs the following means in order to solve the
problems mentioned above.
[0019] (1) A water supplying apparatus for executing a washing
process, a cleaning process and a working process of a subject,
comprising:
[0020] a water vapor body supplying means for supplying a water
vapor body; and
[0021] a water mist body supplying means for supplying a water mist
body containing liquid water fine particles,
[0022] wherein the water vapor body and the water mist body are
supplied to the subject by independently controlling the two
means.
[0023] (2) A water supplying apparatus as recited in the item (1),
wherein the subject includes a disused material of a resist film
and a polymer residue which are generated in connection with
manufacture of a semiconductor device.
[0024] (3) A water supplying apparatus as recited in the items (1)
and/or (2), wherein the water vapor body or the water mist body is
supplied in a state of being contained in a gas.
[0025] (4) A water supplying apparatus as recited in the item (2)
or (3), further comprising a contacting and/or permeating means for
contacting and/or permeating the water vapor body with respect to
the subject, and an injecting means for injecting the water mist
body to the subject, wherein the disused material is removed on the
basis of a cooperation between the water vapor body and the water
mist body.
[0026] (5) A water supplying apparatus as recited in any one of the
items (1) to (4), further comprising a nozzle means for supplying
the water vapor body and/or the water mist body to the subject.
[0027] (6) A water supplying apparatus as recited in the item (5),
wherein the nozzle means is arranged so as to be opposed to the
subject placed within a processing chamber.
[0028] (7) A water supplying apparatus as recited in the item (5)
or (6), wherein the nozzle means is constituted by a two-fluid
mixture injecting nozzle provided with a first flow passage for
passing the water vapor body therethrough and a second flow passage
passing the water mist body therethrough.
[0029] (8) A water supplying apparatus as recited in the item (5)
or (6), wherein the nozzle means is constituted by a two-fluid
mixture injecting nozzle provided with a first flow passage for
passing the water vapor body therethrough and a second flow passage
for passing the liquid water therethrough. In accordance with this
structure, it is possible to generate a water mist containing
liquid water fine particles in a gas by passing the liquid water
therethrough and injecting the liquid water from a discharge
port.
[0030] (9) A water supplying apparatus as recited in the item (7)
or (8), wherein the two-fluid mixture injecting nozzle is provided
with a mixing portion for mixing the water vapor body and the water
mist body.
[0031] (10) A water supplying apparatus as recited in any one of
the items (3) to (9), wherein the gas is constituted by any one of
air, nitrogen, argon, carbon dioxide, ozone and helium, or a
combination of at least two elements.
[0032] (11) A water supplying apparatus as recited in any one of
the items (1) to (10), wherein the water vapor body is controlled
so that a temperature becomes equal to or more than a boiling
point, and the water mist body is controlled so that a temperature
becomes equal to or less than a boiling point.
[0033] (12) A water supplying apparatus as recited in any one of
the items (1) to (11), wherein the liquid water fine particles
contain ozone, carbon dioxide, ion, acid or an alkaline
material.
[0034] (13) A water supplying apparatus as recited in any one of
the items (1) to (12), further comprising an air pressure
controlling means for controlling an inner portion of the
processing chamber in an atmospheric pressure state, a
depressurized state or a pressurized state.
[0035] (14) A water supplying method for executing a washing
process, a cleaning process and a working process of a subject,
comprising the steps of:
[0036] contacting a water vapor body containing vaporized water in
a gas with a surface of the subject and permeating the water vapor
body through the subject;
[0037] injecting a water mist body containing liquid water fine
particles in a gas onto the surface of the subject; and
[0038] removing a disused material from the subject on the basis of
a cooperation between the water vapor body and the water mist
body.
[0039] (15) A water supplying method as recited in the item (14),
wherein the disused material is removed within a chamber an air
pressure of which is controlled in a depressurized state, a normal
pressure state or a pressurized state.
[0040] (16) A water supplying method as recited in the item (14),
wherein the water vapor body is controlled so that a temperature
becomes equal to or more than a boiling point, and the water mist
body is controlled so that a temperature becomes equal to or less
than a boiling point.
BRIEF DESCRIPTION OF THE DRAWINGS
[0041] FIG. 1 is a schematic view showing an embodiment of a nozzle
means employed in a water supplying apparatus in accordance with
the present invention;
[0042] FIG. 2 is a cross sectional schematic view of a two-fluid
mixture injecting nozzle apparatus corresponding to an embodiment
of a nozzle apparatus employed in the water supplying apparatus in
accordance with the present invention;
[0043] FIG. 3 is a cross sectional view of a wafer to which a
resist film is attached, showing an embodiment of a subject to
which a water vapor body and a water mist body are supplied in
connection with the present invention;
[0044] FIG. 4 is an enlarged photograph obtained by photographing a
state that the resist film attached to the wafer changes its nature
due to a process applied by the apparatus in accordance with the
present invention, by using an electron microscope;
[0045] FIG. 5 is a photograph showing a state that the resist film
attached to the wafer is peeled out so as to gradually pass out of
existence;
[0046] FIG. 6 is a view showing a schematic structure of a water
supplying apparatus in accordance with the present invention;
and
[0047] FIG. 7 is a pattern schematic view of a water vapor body and
a water mist body.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0048] Next, a description will be given of an embodiment of a
water supplying apparatus and a water supplying method in
accordance with the present invention with reference to FIGS. 1 to
7.
[0049] FIG. 7 is a view showing a pattern structure of a water
vapor body and a water mist body which are used in the present
invention. The water vapor body in this case generally exists in a
state that heated and vaporized water (vaporized water (H.sub.2O
molecule) is contained in the gas such as air or the like as shown
in FIG. 7(a), however, it is also possible to be constituted by
100% water vapor containing no gas. Further, the water mist body
exists in a state that liquid-like water fine particles are
contained in the gas, as shown in FIG. 7(b).
[0050] In order to generate the water vapor body containing the
vaporized water in the gas, for example, it is possible to generate
by dropping liquid water on a heated plate so as to vaporize this,
and it is also possible to generate by generating the water vapor
so as to heat it. A temperature of the water vapor body is
controlled so as to be equal to or more than 100.degree. under the
atmospheric pressure, preferably between 130.degree. and
160.degree..
[0051] The water mist body can be generated, for example, by
vigorously injecting water at a room temperature or a mixture of
the water and the gas from a nozzle, or can be generated by
utilizing so-called spray principle injecting the gas to a portion
near an injection port of the water.
[0052] Further, it is preferable to set a temperature of the water
mist body to be equal or less than 100.degree. under the
atmospheric pressure.
[0053] In this case, as mentioned below, in the case of applying
the water vapor body and the water mist body to a subject within a
process chamber, it is possible to control an inner portion of the
chamber in the atmospheric pressure state, a depressurized state
and a pressurized state, and in this case, the temperatures of the
water vapor body and the water mist body can be changed by the
pressure within the chamber. Accordingly, the temperature of the
water vapor body can be controlled so as to be equal to or more
than a boiling point thereof, and the temperature of the water mist
body can be controlled so as to be equal to or less than a boiling
point thereof. Further, in the water vapor body containing the
water vaporized in the gas, the vaporized water is normally
contained in the air, however, it is not limited to the air, and a
gas such as nitrogen, argon, helium and the like may be employed.
The same matter can be applied to the air in the water mist
body.
[0054] Further, a method of producing the water mist body including
the liquid water fine particles containing ozone, carbon dioxide,
ion, acid or an alkaline material has the following three ways in a
wide view.
[0055] (1) It is possible to produce the water mist body by using
the liquid water previously containing the material mentioned
above.
[0056] (2) It is possible to produce the water mist body containing
the material mentioned above by being contacted with and absorbed
in the water so as to inject the gas forming the water containing
the material mentioned above from the nozzle together with the
liquid water, thereby generating the water mist body.
[0057] (3) It is possible to produce the water mist body containing
the material mentioned above by being contacted with and absorbed
in the water after making the water mist body containing nothing so
as to be contacted with the gas forming the water containing the
material mentioned above.
[0058] Further, by using the water mist body mentioned above, it is
possible to promote prevention and removal of a charge-up of an
electric charge to the subject during a step of removing a disused
material such as the resist or the like.
[0059] FIG. 1(a) shows an embodiment of a structure of a nozzle
means used in a water supplying apparatus in accordance with the
present invention. In this embodiment, two nozzles 10 and 12 are
independently prepared. Further, a supplied material A is a water
vapor body supplied to the nozzle 10 and a supplied material B is a
water mist body supplied to the nozzle 12. In this case, the nozzle
10 and the nozzle 12 are arranged close to a subject (not
shown).
[0060] The water vapor body injected from the nozzle 10 reaches a
surface of the subject and permeates through the disused material
such as the resist film or the like so as to weaken a bonding force
between the disused material and a substrate on an interface.
[0061] Further, the water mist body injecting from the nozzle 12 is
injected to the surface of the subject accompanied with a
predetermined pressure so as to peel and remove the disused
material such as the resist film or the like having a weakened
bonding force with respect to the interface.
[0062] Further, in accordance with a research and experiment by the
inventors, it is found that a high peeling effect can be obtained
when the temperature of the water vapor body is over 100.degree.
and between 120.degree. and 180.degree. and the temperature of the
water mist body is equal to or less than 100.degree., and it is
possible to realize a removing apparatus of the disused material
such as the resist film or the like with a high efficiency by
controlling so as to set to this condition.
[0063] In the manner mentioned above, in accordance with the water
supplying apparatus of the present invention, the apparatus is
structured such as to properly and effectively supply the water
vapor body and the water mist body to the subject by providing a
means for supplying the water vapor body in one nozzle and
providing a means for supplying the water mist body in another
nozzle, and combining these two means so as to independently
control them.
[0064] In this case, in FIG. 1(a), the description is given on the
assumption that the supplied material A is the water vapor body
supplied to the nozzle 10, and the supplied material B is the water
mist body supplied to the nozzle 12, however, the supplied material
A may be of course the water mist body supplied to the nozzle 10,
and the supplied material B is the water vapor body supplied to the
nozzle 12.
[0065] FIGS. 1(b) and 1(c) show another embodiment of the structure
of the nozzle means used in the water supplying apparatus in
accordance with the present invention. A nozzle 18 in FIG. 1(b) or
a nozzle 16 in FIG. 1(c) corresponds to any one of two nozzles 10
and 12 in FIG. 1(a).
[0066] FIG. 1(c) shows a state that a water mist body c2 itself
produced in the other place for supplying the water mist body c2 is
supplied through the nozzle 16.
[0067] Further, FIG. 1(b) shows a nozzle apparatus having a
structure made such that an inner portion of the nozzle 18 is
separated into a center side supplying portion 18b and an outer
side supplying portion 18b and a water mist body c1 is produced
within the nozzle 18 so as to supply. In order to produce the water
mist body within the nozzle by using the structure mentioned above,
for example, the liquid water and the water vapor may be mixed so
as to produce, or it is possible to produce by mixing the liquid
water and the gas. Accordingly, in the nozzle 18, the structure may
be made such as to respectively supply two kinds of materials to
the center side supplying portion 18b and the outer side supplying
portion 18a in a branched manner, whereby the materials are mixed
near the injection port and the water mist body c1 is obtained.
[0068] FIG. 2 is a view showing an embodiment of the nozzle
apparatus used in the water supplying apparatus in accordance with
the present invention by using a cross section.
[0069] In a nozzle apparatus shown in FIG. 2(a), liquid water in a
high-pressure state is supplied as the supplied material B from a
center supply port e1. Further, the water vapor is supplied as the
supplied material A from a side supply port e2. Further, in a
portion (a portion shown by a dotted circle in the drawing) near a
discharge port of the nozzle apparatus, the water vapor body A and
the liquid water B are mixed, and a water mist body C is formed and
injected from an injection port.
[0070] In the nozzle apparatus shown in FIG. 2(a), one nozzle
apparatus is provided, however, is provided with two means
constituted by a means for supplying the water vapor body and a
means for supplying the water mist body. In this case, the water
mist body C in this nozzle apparatus is not supplied from the other
place after previously produced, but the water mist body C is
produced on the basis of the discharge of the liquid water B.
Accordingly, in this case, by controlling the supply of the water
vapor body A and the liquid water B, it is possible to
independently control the means for supplying the water vapor body
and the means for supplying the water mist body, and two means can
be variously combined.
[0071] In the nozzle apparatus shown in FIG. 2(b), the water vapor
is supplied as the supplied material B from the center supply port
e1. Further, the liquid water is supplied as the supplied material
A from the side supply port e2. Further, in a portion (a portion
shown by reference 14 in the drawing) near the discharge port of
the nozzle apparatus, the water vapor body B and the liquid water A
are mixed, whereby the water mist body C is produced and is
injected out from the injection port 14.
[0072] In FIGS. 2(b) and 2(a), both of the structures are made such
that the water vapor body and the liquid water are respectively
supplied from different supply ports (e1, e2), however, the
apparatuses themselves have no great difference.
[0073] Accordingly, in FIG. 2(b), by controlling the supply of the
water vapor body A and the liquid water B, it is possible to
independently control two means constituted by the means for
supplying the water vapor body and the means for supplying the
water mist body, and two means can be variously combined.
[0074] FIG. 2(c) shows a further nozzle structure. In this nozzle
structure, the water vapor body and the liquid water are not mixed
as is different from FIGS. 2(a) and 2(b), and accordingly, the
mixing portion is not provided. In this case, the structure is made
such that the water vapor body and the water mist body are
respectively discharged to the external portion directly so as to
be injected to the subject. Further, as the supplied material A and
the supplied material B, any one of the water vapor body and the
water mist body is applied as the supplied material, whereby the
nozzle apparatus is structured.
[0075] The nozzle apparatuses exemplified in FIGS. 2(a), 2(b) and
2(c) are called as two-fluid mixture injection nozzles, however, a
shape of the two-fluid mixture injection nozzle capable of being
used in the present invention is not limited to this, and can be
variously modified. In any case, the structure can be employed as
far as it is possible to independently control the amount of
supply, the temperature, the injection pressure of the water vapor
body and the water mist body.
[0076] Then, there is shown here one embodiment among the
researches and experiments executed by the inventors.
[0077] A state that the water mist body (the fine particles) and
the water vapor body (the water vapor gas body) exist together is
prepared by heating pure water of 400 cc/minute by using a pure
water heating apparatus having a processing capacity of 400
cc/minute, and a desirable result of removing a resist film can be
obtained at a time of injecting the water mist body and the water
vapor body to the semiconductor wafer to which the resist film is
attached, via the nozzle apparatus. A weight ratio between the
water vapor body and the water mist body at this time is 25:75.
[0078] FIG. 3 shows an embodiment of the subject to which the water
vapor body and the water mist body are supplied in connection with
the present invention, and is a cross sectional view of the wafer
to which the resist film is attached. The resist film 32, 33 and 34
are closely adhered onto the wafer 30 so as to form hard film
layers, and a thickness thereof is normally about 500 to 800
nm.
[0079] The wafer to which the resist films are attached as shown in
FIG. 3 corresponds to one example of the subject in the water
supplying apparatus in accordance with the present invention, and a
resist film removal after an ion implantation can be significantly
effectively executed by using the water supplying apparatus in
accordance with the present invention.
[0080] The subject is not limited to this, and a polymer residue is
listed up as another example. The polymer residue is generated as a
reaction product at a time of a dry etching, and the polymer
residue can be significantly effectively removed by using the water
supplying apparatus in accordance with the present invention.
[0081] Both of the resist film removal and the polymer residue
removal can be executed at the same time by using the water
supplying apparatus in accordance with the present invention,
however, can be, of course, separately executed.
[0082] In the water supplying apparatus in accordance with the
present invention, there is provided with the means for supplying
the water vapor body (in most cases, including the water vaporized
in the gas) and the means for supplying the water mist body
including the H.sub.2O fine particles, these two supplying means
are independently controlled, and the water vapor body and the
water mist body are directly supplied to the subject.
[0083] Accordingly, at a time of executing the process of removing
the disused material such as the resist film or the like, it is
possible to consider on the assumption of separating the process of
supplying the water vapor body to the wafer and the process of
supplying the water mist body to the wafer. At this time, it can be
assumed that the water gas body is effective for changing its
nature of the resist film or the like due to the permeation of the
gas body, and the water mist body is effective for peeling the
resist film or the like by the fine particles of the water.
[0084] For example, the resist film is formed in manufacturing the
semiconductor device on the basis of a base polymer basic structure
having a hole property and a hydrogen bonding property, and the
resist film body generates physical changes such as softening,
expansion or the like by the high-temperature water vapor body.
Further, a resist permeability of the water vapor body is great,
and the water vapor body generates physical changes such as
swelling, separation, solidification or the like so as to generate
a change in chemical structure. Accordingly, the resist film
hydrated and swelled by the high temperature water vapor body so as
to be softened has a weakened bonding force with the wafer and is
going to be peeled. Further, an injection force or a spraying force
of the nozzle apparatus at a time of supplying the water vapor body
or the water mist body to the subject is applied so as to be
largely effective for peeling the swelled resist and the wafer
substrate.
[0085] The water mist body comes into collision with the particles
attached on the surface at an injecting speed from the nozzle. A
magnitude of the water mist body is set so that a diameter thereof
is about 5 to 50 .mu.m, and on the assumption, for example, of an
injecting speed of about 40 m/second, a colliding force thereof is
sufficient to peel the particles of 0.1 to a few .mu.m from the
wafer base substance.
[0086] FIG. 4 is an enlarged photograph obtained by photographing a
state that the resist film attached to the wafer changes its nature
at a time of executing the process by using the water supplying
apparatus in accordance with the present invention, by using an
electron microscope. As shown in a photograph (a), there can be
seen that when the water vapor body is permeated, changes such as
softening, expansion or the like of the resist film are promoted, a
deformation and a gap are generated from a side of an end portion
between the wafer and the resist film, and the bonding force is
weakened. Further, as shown in a photograph (b) showing the next
stage of the photograph (a), due to a further permeation of the
water vapor body, physical changes such as swelling, separation,
solidification or the like further promote in the resist film body
so as to generate a great crack or the like, and finally the resist
film is peeled out from the wafer in cooperation with an operation
of the water mist body.
[0087] FIG. 5 is a photograph showing a state that the resist film
(pale color portions) attached to the wafer (deep color portions)
is gradually reduced in an order of
(a).fwdarw.(b).fwdarw.(c).fwdarw.(d) and the resist film is peeled
out so as to gradually pass out of existence, at a time of
executing the process of removing the resist film by using the
water supplying apparatus in accordance with the present
invention.
[0088] FIG. 5 is the photograph in accordance with one embodiment
of the present invention, however, in this case, the process of
removing the resist film by using the apparatus in accordance with
the present invention is executed on the basis of the following
conditions. That is, a preset temperature of the water vapor body
is 120.degree., a wafer placing table rotates at 4 rpm, a gap (a
space) of the nozzle is 20 mm, and a flow rate of the pure water is
100 cc per a nozzle.
[0089] FIG. 6 is a view showing one schematic structure of the
water supplying apparatus in accordance with the present invention.
A subject 40 such as a wafer or the like is placed on a rotating
table 50 which rotates about a rotating shaft 60 within a
processing chamber 20. A nozzle means 30 is arranged at a
predetermined interval apart from the subject 40 so as to be
opposed to the subject 40, and a flow passage 32 for supplying the
water vapor body and a flow passage 34 for supplying the water mist
body are mounted to the nozzle means 30.
[0090] At a time of removing the disused material such as the
resist or the like, the water vapor body and the water mist body
are injected from a front end of the nozzle means 30 by scanning
the nozzle means 30 in a radial direction of the subject 40 while
rotating the subject 40 at a predetermined speed so as to execute a
peel-out and a removal.
[0091] In this case, the description is mainly given of removing
the resist film and the polymer residue generated as the disused
material in manufacturing the semiconductor electronic device in
connection with the water supplying apparatus in accordance with
the present invention. However, the range to which the water
supplying apparatus in accordance with the present invention is
applied is not limited to this, and includes a working process in
other electronic devices or the like and a surface precision
treating field, and further, the water supplying apparatus in
accordance with the present invention is greatly effective in
fields of cleaning a substrate, cleaning after a chemical
mechanical polishing (CMP), cleaning a dry etching treated surface,
cleaning a fine circuit, cleaning a mask for forming a fine circuit
and the like.
[0092] As described above, in accordance with the present
invention, since it is possible to independently control the supply
conditions of the water vapor body and the water mist body, the
peeling and removing capacities of the disused material such as the
resist film or the like are high, and it is possible to realize the
effective water supplying apparatus.
* * * * *